Particle Induced X-ray Emission Technique Research Articles

Evaluation of the Effects of High Silver and Copper Nanoparticle Concentrations on Vaccinium myrtillus L. under Field Conditions

The extensive development of nanotechnologies has allowed nanoparticles to impact living systems through different pathways. The effect of single exposure to high concentrations of silver and copper nanoparticles (50–200 mg/L) on Vaccinium myrtillus L. under field conditions was investigated. Nanoparticle uptake in different segments of Vaccinium myrtillus L. was assessed by applying inductively coupled plasma–atomic emission spectroscopy and a particle-induced X-ray emission technique. Copper nanoparticles mainly accumulated in the roots and leaves, while silver nanoparticles showed a higher affinity for the roots and berries. The nanoparticles’ effects on the pigments and antioxidant activity of the plant’s leaves were also evaluated. The possible human health risk associated with the consumption of nanoparticle-contaminated berries was assessed. The results indicated that the consumption of berries contaminated with nanoparticles presented a low risk for human health.

Plant Growth-Promoting Rhizobacteria (PGPR) Reduce Adverse Effects of Salinity and Drought Stresses by Regulating Nutritional Profile of Barley

With the growing emphasis on sustainable agriculture, food security, and environmental protection, the use of beneficial soil microbes is imperative, as the use of chemicals such as fertilizers, pesticides, and herbicides has resulted in food contamination, disease, weed resistance, and negative environmental consequences, which ultimately impacted human health. Climate change is a major factor and is of great concern for crop production. Abiotic stresses, including salt and drought stress, restrain the crop yield. The aim of this particular study is to understand what role do plant growth-promoting rhizobacteria (PGPR) play in combating the salinity and drought stresses through modification of nutritional profile. In the current study, inoculated barley (Hordeum vulgare L.) plants were subjected to various stresses such as 200 mM and 1000 mM salinity stress as well as drought stress, and then their various parameters such as seed germination as well as shoot and root biomasses and photosynthetic activity were compared with non-treated stressed barley plants. Our data depicted an improvement or significant enhancement of these parameters in PGPR (Pseudomonas fluorescens SBW25 and Pseudomonas putida KT2440) applied barley plants. Furthermore, the particle-induced X-ray emission (PIXE) technique was used for the elemental analysis of PGPR-inoculated and non-inoculated plants under stress vs. no stress conditions. Our PIXE analysis of various macro- and micronutrients revealed an enhancement of Ca, Mg, K, P, S, Al, and Si uptake in PGPR-treated plants. PGPR applications depicted reduced Cl− contents in 200 mM salt-stressed barley roots (KT2440 = 7.7 mg/kg and SBW25 = 6.3 mg/kg) and stems (KT2440 = 406.4 mg/kg and SBW25 = 365.5 mg/kg) as compared to controls (roots = 8.9 and stems = 469.5), while they displayed a significant increase in the barley leaves (KT2440 = 405 mg/kg and SBW25 = 416.4 mg/kg) when compared to control (110.6 mg/kg) under the same stress condition. In 1000 mM salt stress, a significant reduction in the Cl− content was observed in PGPR-applied barley roots (KT2440 = 7.6 mg/kg), stems (KT2440 = 1205.8 mg/kg and SBW25 = 1008.3 mg/kg), and leaves (KT2440 = 967.8 mg/kg and SBW25 = 530.8 mg/kg) when compared to controls (roots = 15.2 mg/kg, stems = 1605.2 mg/kg, and leaves = 1165.2 mg/kg). On the other hand, a significant increase in the Cl− content was noticed in PGPR-applied barley roots (KT2440 = 29.5 mg/kg and SBW25 = 25.8 mg/kg), stems (KT2440 = 1023.8 mg/kg and SBW25 = 894.9 mg/kg), and leaves (KT2440 = 369.2 mg/kg and SBW25 = 409.8 mg/kg) when compared to controls (roots = 13.5 mg/kg, stems = 505.3 mg/kg, and leaves = 219.9 mg/kg) under drought stress condition. PGPR application was also found to be effective for enhancing the uptake of micronutrients (Mn, Fe, Co, Ni, Cu, and Zn) in barley plant parts under control and also under stressed conditions. Overall, our findings revealed an improvement in the uptake of macro- and micronutrients for the enhancement of salinity and drought stress tolerance. Conclusively, these PGPR species are an effective source of plant stress tolerance and elevated growth of barley and related plants under stress conditions.

Opto-electronic properties of copper-zinc-sulfide thin films grown via metalorganic-chemical vapor deposition technique at different flow rates

In this work, copper zinc sulfide (CZS) ternary thin films were prepared from the pyrolysis of a Bis-(morpholinodithiato-s,s’)-Cu-Zn precursor using metal-organic chemical vapor deposition technique maintained at 450 °C in ambient nitrogen as the carrier gas. The deposition flow rate was varied to study its effect on the optoelectronic properties of CZS films. The particle-induced x-ray emission technique (PIXE) of the prepared single solid source precursor shows the presence of copper, zinc, and sulfur. The Fourier transform infrared spectrophotometer of the precursor reveals the metal-metal bond attachment to the ligand at a very low wavenumber. The XRD spectra reveal the formation of the hexagonal closed-packed structure of CZS films with a preferred orientation along the [111] direction. The film crystallite size is found to increase from 10.4 to 12.2 nm as the flow rate increases, while the dislocation density and stress decrease as the deposition flow rate increases. The SEM analysis revealed an improvement in the growth rate of the grains as the flow rate increased. The transmittance of the deposited CZS films was found to increase from 58% to 84.2% in the infrared region with an increase in band gap from 3.08–3.64 eV as the flow rate increased. The deposited film shows ohmic properties and an increase in conductivity from 0.243 to 0.847 ( while the resistivity decreases as the flow rate increases. These observations provide room for the deposited CZS film to serve as a potential material for optoelectronics and window layer solar cell devices.

Quantification and speciation of lead in air particulate matter collected from an urban area in Amman, Jordan

Lead (Pb) is a carcinogenic element, and it originates in the atmosphere from various natural and anthropogenic sources. This work aims to provide further insights about the presence of lead in Amman’s atmosphere. Air particulate matter (PM) samples were collected in two fractions (PM2.5 and PM10) simultaneously on Teflon filters in an urban area in Amman, Jordan. Elemental quantification and chemical speciation of Pb were performed using particle-induced X-ray emission (PIXE) and X-ray absorption near-edge structure (XANES) techniques, respectively. Elemental quantitative analysis using PIXE showed that Pb concentrations increased during workdays regardless of the aerosol particle size fraction. The average Pb concentration was 2.9 ± 1.7 ng/m3 and 3.9 ± 2.0 ng/m3 in PM2.5 and PM10, respectively. Based on XANES measurements, it was shown that both PM2.5 and PM10 in Amman contain divalent lead (Pb (II)), most likely as PbSO4, PbS and PbO compounds.

Deposition of heavy metals in biological tissues of workers in metal workshops.

Welding and cutting of metals produce large amounts of particulate matter (PM), which poses a significant health risk to exposed workers. Appropriate biological markers to estimate exposure are of great interest for occupational health and safety. Here, hair and nail samples from metal workers were analyzed, which appear to be more suitable than blood or urine samples for assessing long-term exposure. Four workshops working with steel components were included in the study. The hair and nail samples were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) to measure the concentrations of 12 elements. At the workplaces, the concentrations of 15 elements in particulate matter were determined using X-ray fluorescence (XRF) and particle-induced X-ray emission (PIXE) techniques. The hair and nail samples of the workers contained significantly higher metal concentrations than the analytical results of a nonexposed control group. The most significant difference between the groups was found for Ti, Mn, Fe, and Co.

Characterization of agricultural biomass by particle induced x-ray emission and Rutherford backscattering techniques

Particle-induced x-ray emission (PIXE) and Rutherford backscattering spectrometry (RBS) techniques are non-destructive elemental analyses method with high sensitivity and capability for multi-element analysis in one spectrum. These techniques have not been used for the elemental characterization of biomass. So, this study characterized and evaluated elemental compositions of some selected agricultural biomass (Palm kernel shell (PKS), coconut shell (CS), cassava peel (CP), and Africa star apple seed shell (ASASS)) using combined PIXE and RBS. The results were compared with the ultimate analysis and optical-based techniques. Results from PIXE and RBS analysis confirm the presence of C, O, S, Na, Mg, P, Si, K, Ca, Fe, Cl, Al, Ti, Cu, and Zn in the tested biomass samples. Estimation of RBS accuracy by direct comparison with the ultimate analysis of some biomass samples showed a wide disparity of ±10.7% and ±2.57% in the RBS data for carbon and oxygen in PKS and a disparity of ±5.22% and ±0.55% in the RBS data for carbon and oxygen in coconut shell respectively. In the case of minor and trace element concentrations, estimated errors in the range of 1–3% and 2.68–4% were observed for optically based techniques compared with PIXE and RBS analysis, respectively.

In1-xGaxSb nanofoams made by ion irradiation of sputtered films: Atomic composition and structure

This article reports on the atomic composition and structural changes induced by ion irradiation in In1-xGaxSb films deposited by magnetron sputtering on SiO2/Si. Samples with x values equal 0, 0.2, 0.4, 0.5 and 1 were irradiated with 16 MeV Au+7 ions, in the fluence range 5 × 1013–2 × 1014 cm−2 (3 × 1014 for GaSb) and the structure and atomic composition of the films were investigated. Upon irradiation, all films attain a nanofoam-like structure, and the most pronounced swelling was observed in ternary films with 20% Ga atomic concentration. With particle induced x-ray emission technique, we identified the presence of C, O, Ga, In and Sb, with C and O concentrations significantly higher in the nanofoams, compared to the as-deposited films. Rutherford backscattering spectrometry analysis showed the atomic composition of the ternaries is not uniform, but forms two layers with slightly different relative atomic concentrations, specially after irradiation, with C and O uptake greatly enhanced by ion irradiation, more pronounced towards the surface. Grazing incidence x-ray diffraction analysis revealed that ion irradiation with total fluence of 2 × 1014 cm−2 induces amorphization of the ternaries, except for samples with 50% Ga, which remain polycrystalline, despite the ion-induced porosity.

Quantification of potentially toxic element contamination in groundwater using the novel particle-induced X-ray emission (PIXE) technique and human health impacts

The particle-induced X-ray emission system is an extremely responsive multi-elemental diagnostic practice uses to analyze thin films, air, water, archaeological and biological samples. This complicated system was used to quantify heavy metals presented in groundwater in the South-Central part of Bangladesh. Contaminates in tube-well water are related in a straight line with human health hazard. The study was designed to scrutinize heavy metal concentrations in 170 groundwater samples collected from densely settled area of Gopalganj District, Bangladesh. The samples were collected from 96 No. Fukra, Kurulia and Kandi Tilchara Mouza. The study represents that the highest arsenic concentration was 260 μg/L, iron was 17.21 mg/L, manganese was 0.94 mg/L, zinc was 1.71 mg/L and copper was 0.07 mg/L. The end result evidently showed that almost 5.0 times elevated arsenic concentration, 17.0 times higher iron concentration, 9.0 times elevated manganese concentration were found in the study area as compared to standard value approved by Bangladesh. The peak concentration of arsenic was found in Kandi Tilchchara Mouza, which was along the bank of Madhumati River. The spatial distribution showed that arsenic concentration was relatively towering in Kandi Tilchchara Mouza. Majority of water sources were unsuitable for drinking and cooking in terms of arsenic and manganese concentrations. The cumulative ingestion of drinking water along the study area imposes high non-carcinogenic and very high cancer risk to the residents’ health.

Spatial Evaluation of Health Risk due to Inhalation of PM2.5 Pollutants in the Metropolitan Areas of Toluca Valley and Mexico Valley

Aims: In the present work, health risk from inhalation of PM2.5 pollutants in both areas was assessed spatially
 Place and Duration of Study: The metropolitan areas of the Toluca (MATV) and Mexico Valleys (MAMV), between September and November 2009.
 Methodology: A simultaneous sampling campaign was conducted in the Toluca and Mexico Valleys on alternate days from September-22 to November-29, 2009. From the samples collected, their gravimetric concentration was obtained, and S, Cl, K, Ca Ti, V, Mn, Fe, Ni, Cu, Zn, and Pb were determined using the particle-induced X-ray emission technique (PIXE).
 Results: The health risk by inhalation of PM2.5 with a higher result for the metropolitan area of the Toluca Valley (2.09 for adults, 6.25 for children from 6-12 years old, and 6.58 for children from 2-6 years old) in contrast with that of the metropolitan area of the Mexico Valley (1.67 for adults, 5.20 for children from 6-12 years old, and 5.28 for children from 2-6 years old).
 Conclusion: These results are perhaps due to the higher concentration of Cl and Mn for the MATV. Additionally, the air parcels from sampling site MAMV go to MATV and thus contributes to an increased health risk from inhalation of PM2.5. There are health risks for the inhalation of PM2.5 in the MATV and MAMV study areas. The risk only considers the elemental risk. There are no similar studies for this comparison between MATV and MAMV in the literature.

Ionic Surfactant Enhancement of Clay Properties for Heavy Metals Adsorption: Kinetics and Isotherms

The global health problems arising from ingesting toxic metals necessitate the quest for developing efficient materials for their remediation. Surface properties of raw kaolinite clay collected from Ire-Ekiti, South-western Nigeria, were improved by modification using sodium dodecyl sulphate (SDS) for the adsorptive removal of Pb, Cr, Ni and Cu from their respective aqueous solution. The raw and modified clays were characterized by X-ray fluorescence, Fourier transformed infrared spectrometry, Scanning electron microscope coupled with EDX and Particle induced x-ray emission technique. A batch adsorption study was used to examine the performance efficiency of the modified clay. Optimization of adsorption conditions like temperature, particle size, concentration, agitation time and pH was performed. The clay after modification showed improved surface properties such as increased pore diameter and number. Freundlich, Langmuir and Temkin isotherm models were applied to explicate the adsorption processes, while Pseudo-First order, Pseudo-Second order and the Elovich kinetic models were used to predict possible mechanisms driving the adsorption processes. The adsorption processes driven by chemical mechanisms involved series of complex mechanisms that include ion exchange, direct bonding and surface complexation other than precipitation. The percentage removal of the metals by the modified clay soil reached the values of 98.53, 94.50, 73.82, and 80.40 for Pb, Cu, Ni and Cr.

Elemental concentration of tomato paste and respective packages through particle-induced X-ray emission

The elemental concentrations of three brands of Brazilian tomato paste packed in cans and Tetra Pak® cardboard boxes were determined through the Particle-Induced X-ray Emission (PIXE) technique. The elements Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Br and Rb were identified in the tomato pastes. The metallic cannisters are characterized primarily by the presence of Fe and Sn, while several elements including Al, Cl, Ti, Fe and Zn showed up in Tetra Pak® boxes. The elemental concentrations of tomato paste varied significantly among different brands and packages. The major elements present in tomato paste are Na, Cl and K with concentrations ranging from 1700 mg/kg up to 7500 mg/kg, while trace elements like Br and Rb had average concentrations around 2 mg/kg. Tomato paste from different brands and packages stored for long periods of time were evaluated as well. Canned tomato paste showed distinct rising and decreasing trends of Fe and Al concentrations as a function of the storage time respectively. Possible transfer mechanisms are discussed.

Variance of elemental concentrations of organic products: the case of Brazilian coffee

Elemental composition can be used to help determining the origin and quality of food and beverage. The present study aims to investigate the variation of the elemental composition of a Brazilian coffee brand across different production batches. To that end, 102 samples from 11 different batches of “Melitta Tradicional” roasted ground coffee were analyzed using the Particle-Induced X-ray Emission (PIXE) technique. The concentrations of Mg, Al, Si, P, S, Cl, K, Ca, Ti, Mn, Fe, Cu, Zn and Rb were determined. Differences in the elemental concentrations between at least two batches were observed for all investigated elements but Ti. For elements such as Cl, Ca, Cu and Rb the concentration varied over 50% between batches. The differences observed among batches indicate that the characterization of coffee by brand or origin is not a straightforward task.

Characterization of PM2.5 sources in a Belgrade suburban area: a multi-scale receptor-oriented approach.

Designated as the most harmful for health, PM2.5 aerosol fraction was a subject of our study. It was collected for all four seasons during 2014/15 in the suburban area of Belgrade (Serbia) and analysed for Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, As, Ba and Pb elements and for NH4+, NO3- and SO42- ions by particle-induced X-ray emission and ion chromatography techniques, respectively. Obtained concentrations have been treated by a combination of several receptor-oriented models to reveal source contributions to the suburban PM2.5 at different spatial scales. Applied positive matrix factorization analysis indicated five main groups of emission sources: biomass burning (14.5%), traffic (3.9%), regional combustion/secondary sulphates (28.8%), local combustion/secondary nitrates (29.7%) and soil (5.4%). Local heating units had been pointed out as dominant contributors by long-range transport and ground-wind circulation analyses. Air masses circulating over the Balkan Peninsula denoted regional emissions as responsible for the high concentrations of secondary sulphates. Local and long-range transport analyses combined suggested that the BB and the LC/NO3 originated from the wider urban area. Several Saharan dust episodes were detected as well. Presented results might be a basis for the development of air pollution mitigation strategies in the continental Balkan area, considered one of the most polluted and under-investigated European regions.

Increased Cd2+ biosorption capability of Aspergillus nidulans elicited by crpA deletion.

The P-type ATPase CrpA is an important Cu2+ /Cd2+ pump in the Aspergilli, significantly contributing to the heavy metal stress tolerance of these ascomycetous fungi. As expected, the deletion of crpA resulted in Cu2+ /Cd2+ -sensitive phenotypes in Aspergillus nidulans on stress agar plates inoculated with conidia. Nevertheless, paradoxical growth stimulations were observed with the ΔcrpA strain in both standard Cu2+ stress agar plate experiments and cellophane colony harvest (CCH) cultures, when exposed to Cd2+ . These observations reflect efficient compensatory mechanisms for the loss of CrpA operating under these experimental conditions. It is remarkable that the ΔcrpA strain showed a 2.7 times higher Cd biosorption capacity in CCH cultures, which may facilitate the development of new, fungal biomass-based bioremediation technologies to extract harmful Cd2+ ions from the environment. The nullification of crpA also significantlychanged the spatial distribution of Cu and Cd in CCH cultures, as demonstrated by the combined particle-induced X-ray emission and scanning transmission ion microscopy technique. Most important, the centers of gravity for Cu and Cd accumulations of the ΔcrpA colonies shifted toward the older regions as compared with wild-type surface cultures.

Oxidative Potential Sensitivity to Metals, Br, P, S, and Se in PM10 Samples: New Insights from a Monitoring Campaign in Southeastern Italy

Different analytical techniques were used in this work to investigate the relationships between oxidative potential (OP) and metal, Br, P, S, and Se concentration in PM10 samples. Dithiothreitol and ascorbic acid acellular assays were used to determine the oxidative potential (OP) in PM10 samples. The particle-induced X-ray emission technique was used to estimate the mass concentration of specific chemical elements. PM10 samples were collected in Lecce, a coastal site of the Central Mediterranean away from large sources of local pollution. Both winter and spring samples were analyzed to study the seasonal dependence of the relationships between OP values and chemical element concentrations. The Redundancy Discriminant Analysis (RDA) was applied to (volume- and mass-normalized) OP values as response variables and metal, Br, P, S, and Se concentrations as explanatory variables. RDA triplots allowed to visualize the main relationships between PM10 OP values and corresponding chemical element concentrations. Spearman correlation coefficients were also used to investigate the relationships between OP values and metal, Br, P, S, and Se concentrations, besides comparing RDA outcomes. The integrated approach based on two different techniques allowed to better highlight the potentially harmful effects associated with specific metals and other chemical elements in PM10 samples.

PIXE analysis of blood serum of breast cancer patients undergoing successive chemotherapy

Particle induced X-ray emission technique was used to obtain the serum elemental profile of healthy subjects and breast cancer patients (BCPs) undergoing chemotherapy. Concentrations of elements K, Ca, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Se, Br, Rb, and Sr were determined. The increased levels of Ca, Cr, Fe and Cu and diminished levels of Ti, Zn, and Se observed in BCPs prior to therapy, were restored to near normal levels after the fifth cycle of chemotherapy. This work elicits a unique possibility of identifying novel trace element based anti-tumour drugs for breast cancer.

Scientific investigations on Byzantine pottery from Castellum 22, Romania

Forty five ceramic shards discovered in archaeological excavations at Castellum 22 site, Constanţa County, southeastern Romania, and dated to the 10th–11th centuries AD, were subjected to scientific investigations in order to get clues about the raw materials and manufacturing techniques employed by the potters from the Lower Danube zone at the end of the 1st millennium AD.The analyzed shards were selected according to archaeological criteria. The characteristics of the fabric, such as texture, porosity and microstructure, as well as the surface treatments and firing conditions, were studied using Optical Microscopy (OM).Chemical composition was determined using Particle-Induced X-ray Emission (PIXE) technique at AN2000 accelerator of LNL, INFN, Italy. Principal Component Analysis (PCA) of the PIXE data for the ceramic bodies highlighted two main groups of shards with distinct compositional signatures.Micro-PIXE maps of the interfaces between the olive green or yellow glaze and the underlying ceramic body indicated that the decorative layers are strongly enriched in lead.The results of these investigations were compared to the ones previously obtained on coeval pottery from other archaeological sites, such as Hârşova, Oltina, Păcuiul lui Soare, and Valu lui Traian, in a trial to get some insights about the life and customs of the people from the Lower Danube region during the Byzantine period.

Elemental extraction factor from ground to drinking coffee as a function of the water temperature

Several factors influence the elemental composition of drinking coffee including the method of preparation, the grain size of the ground coffee and the water quality and temperature. In the present study, the extraction factor of elements from ground coffee during the drip brewing process was evaluated as a function of the water temperature. Drip brewing coffee was prepared using Brazilian ground coffee and mineral water temperatures varying from 20 °C to 80 °C. Samples of ground and spent coffee were prepared for each temperature and analyzed with the Particle-Induced X-ray Emission (PIXE) technique. The results indicate different extraction factor patterns for each element despite some similarities among elements were observed. The extraction for K and P from the ground coffee increased linearly up to the water temperature of 45 °C, then reduced from 45 °C to 70 °C, with a slightly increase at 80 °C. Cl and Rb also seem to have similar extraction factor patterns with different extraction levels for each temperature. The absorption of elements from the water by the ground coffee was observed for Ca, Si and Cu. Moreover, K and Cl have the highest extraction ratios from ground to drinking coffee for all temperatures.

Analysis of meteorite samples using PIXE technique

A non-destructive approach to the sample treatment during the analytical process is one of the crucial advantages of the particle induced X-ray emission technique. Rare and precious environmental and space samples can be analyzed in order to evaluate concentrations of individual elements presented in specimens. A non-destructive analysis of two meteorite samples was carried out using 3 MeV protons incident in a narrow ion beam (1.5 mm diam.). GUPIXWIN software package was used for spectra evaluation. Concentrations of several elements (Fe, Ni, Cu and Zn) were determined and quantitative surface elemental distribution maps were constructed.

Particle induced X-ray emission and Rutherford backscattering spectrometry for testing homogeneity of environmental certified reference material candidates

ABSTRACT Taking advantages of non-destructive techniques, between-bottles homogeneity tests were carried out in term of elemental composition of seven certified reference materials (CRMs) candidates using particle-induced X-ray emission technique (PIXE). A combination of PIXE and RBS techniques (Rutherford backscattering spectrometry) was also used for CRMs candidates having biological matrices. The CRMs candidates have the matrices of soil, sediment, dust, fish muscle, leaves and fruit, which will be certified for some major, minor and trace elements. One batch was produced for each CRM candidate, which included 80 bottles. Between-bottles homogeneity tests were performed for each CRM candidate using seven representative bottles. The repeatability of measurements by PIXE and RBS was examined. The relative standard deviations (RSD) and relative average deviation (RAD) of the elements contents were considered for variability assessment for both repeatability and between-bottles homogeneity. Al, Si and Fe showed good repeatability with RSD and RAD of <4%, while Mg, S, Cl, K, Ca, Mn and Sr showed RSD and RAD in the range of 4–10%. A content of one element in the examined CRMs candidates, with the exception of the date fruit, showed RSD and RAD of <5% indicating good between-bottles homogeneity. For date fruit, the relative error of all elements was <10%, with the exception of Si and Zn, while RAD of S, Cl and K were <10%.